Production of metals



A ril- 16, 1946. J. c. MUNDAY PRODUCTION OF METALS 2 Sheets-Sheet 1 Filed July '10,, 1943 5 epa'rafom F- 8 M 5 M w 8 6| a 8 iv 9 a, f g I M Q IV \a, w m 8 m I mum a m w fl 7 I M a 0 c 3 y a, L iv a I 1 a Z w 2 w x a; 3 4/ u n/lllllu/ A TM 1w a! 3 mm m T at... V. I n w a i f W 2/ u w l 8 E a a w 7 5 n. a d Ill 4 J n k k c T 5 3 2 4/ n 9 g M W'L. m

April 16, 1946. J. c. MUNDAY PRODUCTION OF METALS Filed July 10, 1943 2 Sheets-Sheet Z NQT mru I w Patented Apr. 16,

I PRODUCTION OF METALS John C. Munday, Cranford, N.'J., assignor to Standard Oil Development Company, a corporation of Delaware Application July 10, 1943, Serial No. 494,182

9 Claims.

Thepresent invention relates to the art of producing magnesium and other similar metals from their oxides, hydroxide and carbonate ores by reduction, and more specifically, to an improved method of conducting these reactions in a continuous, thoroughly eflicient manner.

The drawing in Fig. 1 is a semi-diagrammatic view in sectional elevation of an apparatus for accomplishing the reduction of magnesia, and indicates the flow of materials through the apparatus; and

Fig. 2 shows a modification of the process.

It is well known that oxides, hydroxides and carbonates of magnesium and other metals of the same class such as beryllium, cadmium, alumi num, zinc and mercury, can be readily reduced to the metallic state by the action-of solid carbon at high temperatures, but the methods now in use are not particularly efllcient and'are generally conducted in batch. The temperature required is extremely high in some cases of the or-v der of 2200 C., and the reaction which involves the concomitant production of carbon monoxide is readily reversible.

One object of the present invention is to de- .Vise an efllcient method for carrying out the reduction of such ores by means of carbon and other reductants continuously and 'efllciently. Other objects will be apparent to those skilled in the art.

The invention will be described with particular reference to the production of magnesium from magnesia and carbon, but it is not limited to these reactants. Referring to the drawing, in Fig. 1 numeral I denotes a feed hopper into which a mixture of magnesia and coke is fed by the screw 2. It is preferred to supply this material in finely divided condition, finer than 50 mesh, say 100 to 200 mesh, but even larger lumps can be used if desired. Hopper I i fitted with a closed top and gas is fed into the bottom by pipe 3. The gas decreases the density of the solids by aeration, and they become capable of flowin much like liquids through pipes, valves and other fittings and show both dynamic and static heads. In thi condition the solids are said to be "fluidized or to be in fluidized condition. Gas is vented-at 5, but it passes through the dust separator 4 so that the solid content is retained in the hopper.

The fluidized solids are thoroughly admixed and are fed down through the standpipe 6 and by way of pipe 1 into a reactor. 35 which is strongly heated, for example by arcs between electrodes 36 and 31, in order to effect the re- 'duction of magnesia by carbon. The product vapors containing magnesium and carbon monoxide are passed from reactor through pipe 38 into a chilling vessel 9. The vessel is called a chilling vessel although its temperature may be from say 300 to 500 C. because the hot stream of products is chilled rapidly therein, in order to prevent reversal of the reduction reaction. This will be described in detail below. The vessel 9 contains a fluidized mixture of carbon and magnesia introduced from hopper I through pipes 6, 1b and 38, and magnesium, which is condensed by the cooling into small particles. The bulk of the gas is drawn ofl from the vessel 9 by a pipe II by way of the dust separator l0 and it is de-.

sirable to provide a secondary separator I 2 so that all of the valuabl magnesium is recovered from the exit gas taken off at Id. The recovered solid is returned to the vessel 9 by the pipe I 3 and the gas may be used for fluidizing purposes or for fuel, as required. The temperature in chiller 9 is maintained as desired by circulating fluidized solids from the chiller through pipe 8, heat exchanger 8a, pipes lb and 38, thence back into the chiller.

From vessel 9 a fluidized stream of solids is taken off by pipe I ,6, and after passingthrough the heater I1 is conducted by the pipes l1 and I8 to a distillation chamber l9 which is maintained at a pressure considerably below atmospheric and is at a point elevated above the vessel 9. Gas such as be added at I 8b. The vapor passe through-the separators 20 and 22 and through the vapor pipes 2| and 24 into one or the other of th -twin receivers25 and 26 which are cooled by coils 21 and 29,-respectively. The receivers are used alternately and are fitted with removable bottoms 3| and 32 for the removal of magnesium. The evacuation pipes 29 and 30 are connected, of course, to the vacuum still which is not shown. The distillation zone I9, like the reducer 35, may be heated directly electrically, if desired.

In the distillation zone magnesium is removed as a vapor, leaving as a residue 9. mixture of carbon and magnesia. The dust separated in the separators 20 and 22 also consists of magnesia and carbon, and these materials are returned to the vessel I 9. These solid residues are in a fluidized state, and as such may be drawn off from the vessel l9 by a pipe 33' and thence returned by 34 to the chiller9. A portion of the fluidized materia1 withdrawn from I9 through pipe 33 may be drawn off from the system by a pipe 4| and th'rough the cooler 42 in order to prevent build-up hydrogen or methane may of non-reducible impurities such as silica, and of excessive amounts of flne or coarse particles outside the desired particle size range. It is also desirable for reactor 35 to have an outlet pipe 44 for the same reason.

In a modification, the magnesia-coke mixture from hopper I may be introduced flrst to chiller 9, rather than directly to reactor 35, by way of pipes 6, 1b and 38, and then passed through pipes 16, I1 and 45 to reactor 35. In this manner the feed materials are used as chilling agents and at the. same time are preheated for subsequent use. Alternately, the feed materials are first passed from chiller 9 to distillation zone It for removal of magnesium, and are then passed through pipes 33, 3|, 40 and 45 to reactor I5. I

The reduction zone 35 is maintained at a temperature of about 2000 or 2200 C. or somewhat higher in order to effect the reaction between the magnesium oxide and carbon so as to produce magnesium vapor and carbon monoxide. Bein vapors, these materials pass rapidly from the reduction zone into the chiller 9 where the reaction products are rapidly reduced in temperature so as to prevent a reversal of the reduction reaction and consequent loss of magnesium. The chiller is ordinarily held at 300 to 500 C. so that the magnesium is condensed and preferably solidified either in small particles or on the surface of the solid materials present. The chilling is rapid and thorough so that little or none of the magnesium once produced is lost by the reversal of the reaction and before reheating the bulk of the CO is separated from the magnesium.

The use of fluidized solids for chilling has important advantages from both-economic and safety standpoints. When gas is used for chilling, as in the prior art, as much as twenty-five volumes per volume of product gases are required, which in turn requires large heat exchangers and dust separators. Furthermore, even a momentary stoppage of the supply 'of chilling gas. allows reversal of the reaction, forming solids from gases, and causing a sharp reduction in pressure which is liable to draw air into the system with consequent danger of explosion. On the other hand, fluidized solids have high heat capacity and the large amount maintained in the chiller acts as a reservoir for heat absorption, so that adequate chilling and perfect fety may be had for hours without any externa cooling whatso-- ever. v

The magnesium content is now separated from the involatile solids by distillation in the vessel l9. Its temperature is maintained from about 750 to 950 C., depending on the pressure which is maintained, but little CO is now present and the reaction is not reversed to any serious degree. The

. important consideration is that the fluidized streams permit flow smoothly and continuously from the chiller tothe distillation vessel is and may be employed in chiller l and distillation chamber l8, respectively, and gas may be introduced wherever required to maintain fluidity.

It is a simple matter to eil'ect th'e fluidization of the solid materials simply by blowing them with a suitable gas. To be capable of flow the solids must contain from, say .01 to .07 cubic feet of gas per pound of the flnely divided solid depending on the density and size range of the particles. Stated in another way, in order to maintain the fluidized condition, the relative superflcial upward velocity of the fluidizing gas through the solids should be of the order of 0.02 to 0.1 feet per second, whereflne powders are employed, and higher when larger lumps are used, say 10 to 20 feet per second for lumps of A to y.

The density of fluidized solids is high, as compared to that of an ordinary suspension or solid in gas, and may be as much as 80% of the free settled density. In the reducer 3-5, the chiller 9 and the distillation zone 1-9 it is preferred to employ gas rates low enough to permit the solids to settle, yet high enough to cause agitation. Zones operated in this manner are termed "hindered settlers and the temperatures therein are quite constant even when conducting highly endothermic or exothermic reactions, or when hot or cold streams are continuously added and withdrawn, as in the present process. Where fine powders are employed, the upward gas velocity in hindered settlers is generally less than 5 feet per second, preferably less than 2 feet per second, and in case very low entrainment is desired, as from distillation zone is, less than 1 foot per second.

It has been found that when an amount of gas over and above that required for fluidizing is added to a fluidized mixture, the only important result is the reduction of the density of the fluidized solids and this fact is taken advantage of to effect the flow of fluidized streams through the equipment. In further explanation, it should be noted that the density of the stream in the pipe i6 is considerably greater than in theopposite pipe i8 because of the gas added at lab and also because of the fact that the pressure in It is lower than that in 9. The flow can be readily controlled by a valve Ila in the pipe 11. As another example, the density of the stream flowing in the pipe 33 is greater than that in I8 and.also greater than the average densityin reactor 35 and in the pipe 38. Thus the flow is effected without the use of blowers or fans operating on the solid streams and merely materials to the several zones, and the amount,

thence from l9 to the reducing vessel 35 or to the I chiller 9.

In the above manner the process is made fully continuous and magnesium is produced rapidly and is then withdrawn and conserved.

In the above mentioned system the solid materials are maintained in a fluidized state throughout. The solids in reactor 35 are fluidized by the CO and Mg vapors formed in the reaction.

However, in order that the solids be fluidized over the whole cross section it is preferable to introduce additional fluidizing gas, for example hydrogen, through pipe 38 beneath distribution grid 40. Similarly, distribution grids l5 and I3 the density and the level of the solids therein, can be controlled and kept in balance by manipulation of the valves and of the quantity of fluidizing gas employed in the various parts of the system. The system is preferably operated on magnesium ores rich in magnesium oxide, l vdroxide or carbonate, but even dolomites containing calcium oxides may be used and a portion of the circulated material would then be drawn ofi continuously or at intervals in order to prevent the building up of calcium oxide and other inert materials in the system.

The apparatus illustrated in Fig. 2 is in many respects quite similar to that already described in operation,

dust separator 58 and is taken oil by the pipe 59, while the remainder of the highly heated coke is fed to the reduction vessel 35 by means of the pipe Bll. A part of the carbon may be fed directly from the hopper through pipe GI and thence to the chiller 9 along with the magnesia if desired.

The reducer 35 in Fig. 2 is similar to that shown in Fig. 1, except that it is shown as heated by resistance or induction coils 62 instead of by electrodes.

The remainder of the apparatus is practically identical with that shown in Fig. l, with the exception of the magnesium recovery system, and has been similarly numbered. The operation of the apparatus shown in Fig. 2 is also similar to that shown in Fig. 1 and needs no detailed description. By supplying a combustion zone, it is possible to furnisha part, at

least, of the heat required for the conversion cheaply by means of the combustion of the coke, whereas in Fig. 1, it is supplied exclusively by electrical means.

With regard to the method of recovering magnesium illustrated in Fig. 2, the flow rate of the magnesium vapor passing overhead from zone I9 is maintained very low so that little contaminant is entrained. If desired, a refractory filter maybe employed to remove traces. The

magnesium vapor is passed through lines 53 and 64 to a hindered settling condenser 65 which contains cool flnely divided magnesium. The magnesium vapors are condensed and solidified either in the form of small particles or on the surface of other particles, and the product magnesium in finely divided fluidized state is drawn off through pipe 66, passed through cooler 67 and withdrawn from the system at 68. A portion of the cool stream is recycled to condenser 65 through pipe 69 for cooling purposes. Additional gas, such as hydrogen, may be introduced to the condenser 65 through pipe 10 if required in order to maintain hindered settling, and gas is removed overhead through pipe 1| where magnesium fines are separated. This method of recovering magnesium allows the dust separation equipment to be operated on a cool gas stream, is continuous passed in fluidized state to storage or to melting retorts.

It will be understood that heat can be recovered from various streams in the process,'for example, the carbon monoxide drawn off from the chiller is at a relatively high temperature, and if desired, its heat can be recovered. Furthermore, it is possible to utilize a part of the heat contained in the products of reaction for reheating the chilled material to effect distillation of the magnesium. Other points of heat recovery will be readily observed by those skilled in the art. The method of cooling the heat exchanger 6'! of-Fig. 2 is of interest. A fluidized stream of an inert solid, for example sand, is circulated through the exchanger and through through and yields a product which can be The present process is operated at a relatively low pressure, ordinarily atmospheric pressure or a few pounds above atmospheric, and no great problems arise in this connection. The chiller, the distillation apparatus and the associated Pipes can be lined with firebrick or other inert refractories. The reducer is best made with carbon, graphite or silicon carbide because of the high temperature and the reactivity of the magnesia at that temperature.

An important feature of the present invention lies in the relative position of the distillation zone in respect to the chilling and reduction zones. It is preferred to locate the distillation zone at a considerably higher level so that the back pres sure resulting from the static head of the fluidized solids in pipe I8 acts to throttle the pressure down to the low value required for distillation in the vacuum, and at the same time, the height of the standpipe 33 is such that suflicient pressure is built up therein to carry the fluidized stream back to the chiller 9 or to the reducing vessel 35.

The process has been described entirely in reference to its application to the manufacture of magnesium, but it will be understood that the process can be readily applied with suitable modiflcations that will be apparent to those skilled in the art of the manufacture of other metals, especially those mentioned herein above.

I claim:

1. An improved process for manufacturing metals of the right hand side of group 2 of the periodic table whose oxides. hydroxides and carbonates are reducible by carbon, which comprises passing a fluidized stream of the reducible metalbearing compound and carbon through a high temperature reaction zone wherein a reducing temperature is maintained and the metal product is vaporized, rapidly chilling the affluent vapor product containing the reduced metal and carbon monoxide by the addition thereto of the cool fresh metal-bearing'compound and carbon fed to the system, separating the bulk of the carbon monoxide from the chilled material, distilling oil the metal and then passing the undistilled mixture of metal-bearing compound and carbon to the reducing zone.

2. Process according to claim 1, in which the solid materials are maintained throughout in a fluidized condition.'

3. Process according to .claim 1 in which a fluidized stream of the metal-bearing compound and carbon is continuously circulated through a circuit comprising a reducing zone, a chilling zone and a distillation zone and in'which the cool fresh metal-bearing material is supplied to the chilling zone continuously and in an amount and at a temperature to reduce the product temperature rapidly and thus prevent reversal of the reaction, and in which the reduced metal is continuously vaporized from the distillation zone.

4. Process according to claim 1 in which the distilling zone is located at a more elevated level 4- aaeaus than the distillation and reaction zones and at a lower pressure.

5. Process for producing magnesium which comprises continuously passing a mixture of magnesia and carbon through a reduction zone at a temperature of the order-of 2200 C. whereby magnesium metal is produced along with carbon monoxide and the former is vaporized and passing the vapors into a chilling zone, continuously passing a mixture of cold magnesia and carbon in a fluidized condition into the chilling zone whereby the temperature is reduced to prevent reversal of the reduction and condense the magnesium vapor, continuously passing a stream of fluidized chilled solids from the chilling zone to a, distillation zone and distilling the magnesium from the fluidized solids therein, and then passing this distillation residue consisting of a mixture of carbon and magnesium continuously to the reduction zone,

6. Process according to claim 5'in which the reduction zone is heated electrically.

7. Process according to claim 5 in which a fluidized stream of carbon is partially burned to produce a high temperature, passing a stream of highly heated, fluidized carbon to the reduction zone and feeding cool fluidized magnesia to the chilling zone.

8. Process according to claim 5 in which the distillation zone is located at a level more elevated than the chilling and reduction zones and is operated at a reduced temperature, the difference in elevation being suflicient when. suitable adjustment is made in the densities of the fluidized streams to cause circulation of the fluidized streams from the distillation to the chilling zone and from the latter to the reduction zone and thence returning to the chilling zone.

9. Process for producing beryllium which comprises continuously passing a mixture of beryllia and carbon through a reducing zone at a temperature above the boiling point of beryllium whereby the beryllium is produced along with carbon monoxide and the former is vaporized, and passing the vapors into a chilling zone, continuously passing a, mixture of cold beryllia and carbon in a fluidized condition into the chilling zone whereby the temperature is reduced to prevent reversal of the reduction and condense the beryllium vapor, continuously passing a stream of fluidized chilled solids from the chilling zone to a distillation zone and distilling the beryllium from the fluidized solids therein and then passing this distillation residue consisting of a mixture of carbon and beryllium continuously to the reduction zone.

JOHN C. MUNDAY. 

